Mild Combustion of non-conventional and liquid fuels. Marco Derudi Dipartimento di Chimica, Materiali e Ingegneria Chimica / CFALab

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Mild Combustion of non-conventional and liquid fuels Marco Derudi Dipartimento di Chimica, Materiali e Ingegneria Chimica / CFALab

INTRODUCTION 2 Combustion processes are essential for power generation, thus the development of a combustion technology able to accomplish improvement of efficiency with reduction of pollutants emissions, as NOx and soot, is a main concern. To improve the thermal efficiency of combustion processes, in the 80 lots of studies were focused on Heat Exchange and Heat Recovery problems.

THE BIRTH OF MILD COMBUSTION 3 Excess enthalpy combustion 1 Heat-recirculating combustion: the exhausts can be used to preheat the reactants upstream the flame region 2 1 Lloyed, Weinberg, Nature, 251,1974 2 Weinberg, Combust. Sci. Technol., 121, 1996

PRELIMINARY ISSUES 4 Advantages Thermal efficiency is increased Reduced fuel consumption Possibility to burn low-calorific fuels Drawbacks Very high peak temperatures High NOx emissions (thermal-nox) Critical design of the burner

NOx CONTROL STRATEGIES 5 Flame control - Temperature - Stoichiometry - Species dilution and scavenging Post-flame control Post-flame NOx reduction by - Reburning - Non-catalytic selective reduction - Catalytic selective reduction (SCR) Choi, Katsuki, Energy Conv. Management, 42, 2001

LOW-NOx BURNERS 6 NOx-control strategies by burner design: - Staging - Swirling - Recirculation These techniques effectively control: - Flame core stoichiometry - Peak flame temperature

RECIRCULATION vs FLAMMABILITY 7 Wünning & Wünning, Prog. Energy Combust. Sci., 23, 1997 %fuel LFL UFL Auto Ignition FP AIT T

DILUTION, PREHEATING, HIGH-MOMENTUM JETS 8 Traditional flame Mild Derudi et al., 6 th HiTACG Symposium, 2005 Milani, Saponaro, La Termotecnica, 1, 2000

ADVANCED LOW-NOx TECHNOLOGY 9

REGENERATIVE BURNERS - 1 10

REGENERATIVE BURNERS - 2 11

SELF-RECUPERATIVE BURNERS 12 combustion chamber recuperator FLOX burner, WS GmbH

ONE TECHNOLOGY, MANY NAMES 13 Heat-recirculating combustion Preheated air combustion (PAC) Diluted Combustion Noiseless combustion High temperature air combustion (HiTAC) Flameless oxidation MILD combustion (Moderate or Intense Low oxygen Dilution)

WHY FLAMELESS? 14 Natural Gas 48MWth Fuel Fuel Fuel TEA swirl burner (ANSALDO) internal recirculation

MILD COMBUSTION - DEFINITION 15 = 1500 K = 1000 K = 550 K T decreases by increasing dilution Derudi, Villani, Rota, Proceedings of the Combustion Institute, 31, 2007 Traditional combustion T Self-Ignition MILD COMBUSTION T inlet > T SI and T < T SI [K] Cavaliere, de Joannon, Prog. Energy Combust. Sci., 30, 2004

TYPICAL EXPERIMENTAL TRENDS 16 Krishnamurthy et al., Proceedings of the Combustion Institute, 32, 2009 MILD Szego et al., Combust. Flame, 154, 2008

LAB-SCALE MILD BURNER 17 Laboratory-scale burner is constituted by three main sections: feeding and pre-heating burner sampling and measurements Lab-scale burner advantages: low-cost low-time high flexibility

LAB-SCALE BURNER: DILUTION RATIO 18 Industrial burner Lab-scale burner k v M e = M + M a M e = recycled exhaust gases stream M a = primary air inlet stream M f = fuel inlet stream f k v R SA IA (1 + R) = + 1 + SA (1 + FA) (1 + SA) SA = 2 ary /1 ary air volumetric ratio IA = inert/1 ary air volumetric ratio FA = fuel/air ratio R = recycle factor

DILUTION RATIO - K v 19 SN: 25% of air external to the nozzle k V = A ρ v E m& F E da SN: 80% of air external to the nozzle Dilution ratio induced by the jets as a function of the dimensionless distance from the air nozzle

HYDROGEN ENRICHED FUELS 20 H 2 -enriched fuels are interesting: greenhouse gases from solid fuels (e.g. coal/biomasses gasification) byproducts of industrial processes (e.g. coke oven gas) BUT H 2 shows properties that make conventional burners unsuited: alternative technologies (MILD) need of research (little work on H 2 enriched fuels )

RESULTS: CH 4 /H 2 21 Temperature OH (flame marker) CH 2 O (ignition marker) Measured T [K] 1279 1321 1363 Predicted T [K] 1273 1368 1375 1390 K Y OH 5.0E-4 Y CH2O 9.3E-5 1270 K 0 0

RESULTS: CH 4 /H 2 22 Temperature predicted with EDC and DRM-19 flame 300K 2190 K 1270 K 2000 K 1270 K 1440 K MILD 1270 K 1390 K

MILD COMBUSTION OF H 2 ENRICHED FUELS: NOx 23 Contribution of different formation routes to the total NO emissions (dry basis) with CH 4 /H 2 mixture for different dilution ratios, kv NNH intermediate mechanism: N 2 + H NNH NNH + O NH + NO Galletti, Parente, Derudi, Rota, Tognotti, Int. J. Hydrogen Energy, 34, 2009

TOWARD A MILD COMBUSTION OF LIQUID FUELS 24 Retrofit a lab-scale burner developed for mild combustion of gases in order to use liquid fuels - Different nozzles configuration - Atomizer for the direct liquid fuel feeding Definition of an experimental procedure for tests with liquid fuels (n-octane, n-dodecane, ) Evaluate main characteristic parameters for mild combustion of liquids requirements for real-size burners design Preliminary definition of operating maps for pure (noctane) and practical (kerosene) fuels

LAB-SCALE MILD BURNER LAYOUT 25 Upper oven for heat maintenance Exhausted gases outlet Quartzwool insulation Thermocouple Liquid Fuel inlet Gaseous Fuel inlet Refractory insulation Preheating oven Secondary air inlet Primary air + inert inlet

LIQUID FUEL ATOMIZATION 26 A pneumatic atomizer (supported by a nitrogen stream), water-cooled to avoid fuel pyrolysis, was developed to create a short fuel jet Cooling water inlet Cooling water outlet Liquid fuel inlet Nitrogen inlet The liquid fuel is sprayed directly into the burner

EXPERIMENTAL PROCEDURE 27 The burner cannot be fired directly with a liquid fuel, so the fuel feed is varied once stable mild combustion conditions are achieved with a gaseous fuel (CH 4, C 2 H 6 ). Average Furnace Temp. Flame Combustion Mixed zone B C Thermal NO x Mild clean Extinction D High CO emissions CD BA Preheating Firing Increase Transition with of to the CHmild 4 dilution or C 2 H 6 Gaseous Gaseous Fuel 2ary fuel 2ary air air 1ary Air air A Kv can be modulated in a wide range K V Kv = ( M + M + M ) R M a1 f i a2 M + M + M a1 a2 f

MIXED ZONE: ROAD TO MILD 28 T [ C] 950 900 850 800 750 A C 700 650 T top B T half 600 T bottom 550 0.0 2.0 4.0 6.0 8.0 10.0 12.0 Kv Thermal gradients smoothing A Flame Combustion B Transition C onc e ntra tion [ppm ] 80 60 40 20 0 A B C 0 2 4 6 8 10 12 Kv NO CO C Clean mild combustion NO < 30 ppm CO < 50 ppm

GAS TO LIQUID TRANSITION 29 Dual nozzle (DN) Single nozzle (SN) Liquid fuel Dual nozzle (DN) Gaseous fuel 1ary air Liquid fuel Gaseous fuel 1ary air HYBRID FUEL FEED: GAS and LIQUID 1ary air PURE METHANE OR ETHANE PURE LIQUID FUEL

n-octane COMBUSTION 30 K V =8.75, air excess=14%, air preheated @ 950 C 1050 1000 T [ C] 950 900 850 T half 800 T top 750 0 20 40 60 80 100 SN % n-octane DN Temperature increase due to the different thermal input Low thermal gradient Concentration [ppm] 20 18 16 14 12 10 8 6 4 2 0 0 20 40 60 80 100 % n-octane NO CO Stable Mild clean regime during and after the gas to liquid fuel transition NO < 30 ppm and no CO emissions during the transition

TEMPERATURE PROFILES 31 K V =8.75, air excess=14%, air preheated @ 1100 C K V =5.6 Preheated air nozzle Exhausts exit K V =2.7

MILD CLEAN REGION: n-octane 32 1050 1005 C 1000 T [ C] 950 900 K V =1.5 850 840 C 800 0.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 Kv

REFERENCE COMPONENTS IN REAL FUELS 33 Concawe, Fuel quality, vehicle technology and their interactions, Report 99-52, 1999 Typical composition of a kerosene 3% Indanes Indenes and Tetralines 16% Alkylbenzenes 5% 2-3 ring aromatics 20% iso-alkanes 34% Cyclo-alkanes 22% n-alkanes Ranzi, Energy&Fuels, 20, 2006

INFLUENCE OF REFERENCE COMPONENTS 34 14 12 Branched hydrocarbons NOx (ppm dry) 10 8 6 4 2 0 n-c8 n-c8/i-c8 95/5 n-c8/i-c8 60/40 0 20 40 60 80 100 liquid fuel (%) Cyclic hydrocarbons 1400 1200 1000 NO Cyc-C6 10% Cyc-C6 20% Cyc-C6 CO [ppm] 800 600 400 200 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Air excess [%]

KEROSENE 35 Kerosene contains not only linear chain and branched molecules, but also alkylbenzenes and other cyclic compounds. GC-MS Analysis C 12 C 11 Main fraction: C 10 - C 13 hydrocarbons C 10 C 13 C 14 C 9 C 15 C 8 C 16

KEROSENE COMBUSTION 36 CO [ppm] 600 500 400 300 200 100 CO (1100 C) CO (950 C) OPTIMAL AIR EXCESS Lower CO emissions found for lower air preheating temperatures (it is increased the reactants residence time into the combustion chamber) 0 13 15 17 19 21 Air excess [%] No CO emissions for air excess larger than 20% Concentration [ppm] 20 15 10 5 0 SN NO CO SOx 0 20 40 60 80 100 % kerosene DN CH 4 to KEROSENE TRANSITION NO < 30 ppm and CO < 1 ppm during the transition SO X emissions (max 2 ppm) K V = 9, air excess=20%, air preheated @ 1100 C

MILD CLEAN REGION: KEROSENE 37 1100 1050 1060 C 1000 T [ C] 950 900 K V =1.7 850 850 C 800 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 Kv

CONCLUSIONS 38 Successful retrofit of a mild combustion burner designed for gaseous fuels to operate with liquid fuels. These tests evidenced that it is possible to change, also during a run, the fuel feeding strategy without affecting the mild sustainability. Separated nozzles can help to realize mild combustion at lower Kv with respect to the SN layout, thus foreseeing the possibility to obtain mild combustion of liquid wastes and/or high reactive fuels (at moderate/high air temperatures and velocities) at low dilution ratios. Operating parameters for burners design

DEVELOPMENTS 39 Mild combustion of liquid wastes Coal mild combustion Biomass mild combustion Stadler et al., Proceedings of the Combustion Institute, 32, 2009

AND FUTURE PERSPECTIVES 40 OXY-fuel mild combustion High-pressure mild combustion (?) Kim et al., Proceedings of the Combustion Institute, 31, 2007 OXY-coal mild combustion (?)